O-aryl o-alkyl s-organo phosphorothidates

ABSTRACT

X being phenyl, phenylalkyl, alkoxy, dialkylamino, acylamido or halogen, provided that at least one X is group other than halogen atom, and n being an integer of 1 - 5. These organic phosphorothiolates can be obtained by reacting a thionophosphate having the formula, WHEREIN R and B are as defined above, with an alkali hydrosulfide having the formula,     WHEREIN R is lower alkyl; A is alkyl, alkenyl, alkinyl, haloalkyl or phenylalkyl; B is a group of the formula,   Novel organic phosphorothiolates, which have both strongly insecticidal and fungicidal activities and low toxicity to mammals, having the formula,

United States Paten n 1 Tsuchiya et al.

[54] O-ARYL O-ALKYL S-ORGANO PHOSPHOROTHIDATES [75] Inventors: Hiroshi Tsuchiya, Ashiya-shi; Kunio Mukai, Nishinomiya-shi; Akio Kimura, Ikedo-shi; Suminori Kawano, Minoo-shi; Keimei Fujimoto, Kobe; Toshiaki Ozaki, Yamamoto, Sigeo; Yositosi Okuno, Toyanaki-shi; Katsutoshi Tanaka, Takarazuka-shi; Tadashi Ooishi; l-Iisnmi Takeda, both of Minoo-shi, all of Japan [73] Assignee: Sumitomo Chemical Company, Ltd.,

Higashi-ku, Osaka, Japan [22] Filed: Nov. 3,1969 [21] 'Appl. No.: 873,503

[30] Foreign Application Priority Data Nov. 12, 1968 Japan ..43/82963 Nov. 14, 1968 Japan ..43/83366 [521 US. Cl. ..260/964, 260/944, 260/945,

Primary Examiner-Lewis Gotts Assistant Examiner-Anton H. Sutto AttorneyStevens, Davis, Miller & Mosher [451 Apr. 3, 1973 57 ABSTRACT Novel organic phosphorothiolates, which have both strongly insecticidal and fungicidal activities and low toxicity to mammals, having the formula,

wherein R is lower alkyl; A is alkyl, alkenyl, alkinyl, haloalkyl or phenylalkyl; B is a group of the formula,

X being phenyl, phenylalkyl, alkoxy, dialkylamino, acylamido or halogen, provided that at least one X is group other than halogen atom, and n being an integer of 1- 5.

These organic phosphorothiolates can be obtained by reacting a thionophosphate having the formula,

s R0)i=i -0-'B (II) wherein R and B are as defined above, with an alkali hydrosulfide having the formula,

M SH I m wherein M is an alkali metal, thereby forming V a thiophosphate having the formula, i

wherein B, R and M are as defined above, and then condensing said salt with a halide having the formula,

Y A V wherein Y is halogen; and A is as defined'above.

5 Claims, No Drawings O-ARYL O-ALKYL S-ORGANO PHOSPHOROTHIDATES This invention relates to novel organic phosphorothiolates. Further, the present invention pertains to a process for preparing said novel organic phosphorothiolates and to insecticidal and fungicidal compositions containing said compounds as active ingredients.

More particularly, the invention is concerned with novel organic phosphorothiolates having the formula,

wherein R is C -C alkyl; A is C C alkyl, C -C alkenyl, C -C alkinyl, C,-C haloalkyl or C -C phenylalkyl; B is a group of the formula,

X being phenyl, C/ -C phenyl-alkyl, C -C alkoxy, C -C dialkylamino, C -C acylamido or halogen atom, provided that at least one X is group other than halogen atom; and n being an integer of l 5; a process for preparing said compounds; and insecticidal and fungicidal compositions containing said compounds as active ingredients.

0,0-Dimethyl-O-p-nitrophenylphosphorothioate and organomercury preparations, which are used in large quantities at present, are high in toxicity to mammals, though strong in insecticidal and fungicidal action, and, therefore their agricultural use has come into question.

An object of the present invention is to provide novel compounds which are strong in both insecticidal and fungicidal action but are low in toxicity to mammals and contain no such heavy metal as in the case of mercury preparations.

Another object of the present invention is to provide a process for preparing novel insecticidal and fungicidal compounds.

A further object of the present invention is to provide excellent insecticidal, fungicidal compositions.

Other objects of the present invention will be apparent from the following description.

In order to accomplish these objects, the present invention provides novel organic phosphorothiolates of the formula (I).

Further the present invention provides a process for producing novel organic phosphorothiolates of the for- .mula (I), which comprises reacting a thiophosphate having the formula,

wherein R and B are as defined previously, with an alkali hydrosulfide having the formula,

M -SH Ill wherein M is an alkali metal, to form a thiophosphate having the formula,

RO/ s wherein R, B and M are as defined previously: andthen Y -A v wherein Y is a halogen atom; and A is as defined previously.

Furthermore the present invention provides insecticidal and fungicidal compositions containing, as active ingredients, novel organic phosphorothiolates of the formula (I).

The organic phosphorothiolates of the formula (I) have insecticidal actions and are able to completely and advantageously control agricultural and sanitary injurious insects. They are as strong as 0,0-dimethyl- O-(3-methyl-4-nitrophenyl)-thiophosphate or 0,0- diethyl-0-(4-nitrophenyl) thiophosphate and are applicable to various insects of a wide scope. That is, they show activities not only to rice injurious insects such as rice stem borers planthoppers and leafhoppers but also to injurious insects belonging to the orders Coleoptera, Lepidoptera and Diptera, and to plant parasitic nematodes. Particularly, the present compounds are characteristic in that they show strong toxicity against mites and scale insects, and that they show marked activities to beetles such as adzuki bean weevils, rice weevils and leaf rollers.

Further, the present compounds have fungicidal effects on various plant diseases and show prominent controlling effects to rice blast, rice Helminthosporium leaf spot, rice sheath blight, and the like. The present compounds have both insecticidal and fungicidal actions and hence can simultaneously control both plant diseases and injurious insects. This is an excellent point which has never been seen heretofore.

The present compounds do not contain such heavy metal as in the case of mercury preparations, nor show such strong acute toxicity as in the case of 0,0-diethylo-(p-nitrophenyl)-thiophosphate but are less toxic, and

. fungicidal compositions high in effects of controlling Compound Number Structural formula N C 133 L O O-i- 'S see-CiHn O-E-S-see-CcHi Q Q Eri'fififi Structural formula ifir Structural formula 3 OCH: 16

I o OiSCH2CHr- 5 O CzHs \P% 4 (1)0113 0 cgmo S-secC'4Hu O I S-sec-C4Hv 17 C2Hr l0 OH --Oi Ssec-C4Hv P $C2Hs CzH O S -11CaH7 6 a 1s OH,OONH O P s CH, I

002135 0 o 7 0 CH3 P o l -s-cmc=cm C3H5O/ s-cmomcl bczHs 19 8 CHa Q o-i -s-cmom- C2H5O/ SCHzCH2- 9 0 In the present invention organic phosphorothiolates are produced as follows:

CzlIrgO Alkali metal hydrosulfide is prepared by introducing hydrogensulfide into a solution of alkali metal hydroxide until the solution is saturated by hydrogensulfide. Examples of the solvent used in this procedure include alcohols such as methanol, ethanol or methyl cellosolve, water, dimethylformamide and dimethyl sulfoxide, and those of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Into the thus obtained solution of alkali metal hydrosulfide, 1 mole of thionophosphate of the formula (II) per 1 mole of the alkali metal hydroxide is added, and the resultant reaction mixture is stirred with heating to result in dealkylation of the thionophosphate and to obtain crystals or viscous oily substance of thiophosphate of the formula (IV). After or without isolation, the thus obtained thiophosphate of the formula (IV) is subjected to condensation reaction with halide of the formula (V) by contacting 1 mole of the thiophosphate with 0.9-1.3 mole of the halide in the presence or absence of a suitable solvent.

Examples of the solvent used include alcohols such as methanol or ethanol, ketones such as acetone or methyl ethyl ketone and water.

After the completion of the condensation reaction, the solvent is removed under reduced pressure, an organic solvent such as toluene is added into the obtained residue, the resultant solution is washed throughly with a diluted aqueous alkaline solution such as'a diluted aqueous sodium carbonate solution, and with water, and then the organic layer is dried over a drying agent and concentrated by removing the solvent under reduced pressure to give the objective organic phosphorothiolate in good yield. The thus obtained organic phosphorothiolate is sufficiently pure, but, if necessary, may be purified by column chromatograph or vacuum distillation.

In the dealkylation of the present invention, reaction temperature and reaction time depend on the kind of the starting materials and the solvent used, but, in generally, the reaction requires the boiling point of the solvent and several or several tens hours. In the condensation reaction of the present invention, the reaction requires, for example, 30 100C. and several hours. In this step, employment of a catalytic amount of iodine may result in a good yield of the reaction.

Examples of the starting materials employed in the present invention, i.e., thionophosphates, hydrosulfides and halides are as shown below. Thionophosphates:

0,0-Dimethyl-O-( 4-phenylphenyl)thionophosphate.

- 0,0-Dimethyl-O-(4-benzylphenyl)thionophosphate.

0,0-Dimethyl-O-(2-chloro-4-phenylphenyl)thionophosphate. 0,0-Dimethyl-O-(2-methoxyphenyl )thionophosphate. O ,O-Dimethyl-O-[ 3-(N,N-dimethylamino )phenyl] thionophosphate. 0,0-Diethyl-O-(4-phenylphenyl)thionophosphate. 0,0-Diethyl-O-(2-phenylphenyl)thionophosphate. 0,0-Diethyl-O-(2-chloro-4-phenylphenyl )thionophosphate. 0,0-Diethyl-O-(4-benzylphenyl)thionophosphate. 0,0'-Diethy1-O-[3-(N,N-dirnethylamino)phenyl ]thionophosphate. 0,0-Diethyl-O-(4-acetamidopheny1)thionophosphate. 0,0-Diethy1-0-(4-methoxyphenyl)thionophosphate. 0,0-Diethyl-O-(Z-rnthoxyphenyl)thionophosphate.

O,O-Di-n-propyl-O-(4-phenylpheny1)thionophosphate. 0,0-Di-n-propyl-O-(2-chloro-4-pheny1phenyl)thionophosphate. 0,0-Dimethyl-O-(B-naphthyl )thionophosphate. 0,0-Dimethyl-O-(B-naphthyl)thionophosphate. 0,0-Diethyl-O-(a-naphthyl)thionophosphate. 0,0-Diethy1-O-(B-naphthyl)thionophosphate.

O,O-Di-n propyl-O-(a-naphthyl)thionophosphate.

0,0-Di-n-propyl-O-(fl-naphthyl)thionophosphate.

0,0-Di-n-butyl-O-(a-naphthyl)thionophosphate. 0,0-Di-n-butyl-O-(B-naphthyl)thionophosphate. l-lydrosulfides;

Sodium hydrosulfide.

Potassium hydrosulfide.

Halides:

Methyl bromide.

Ethyl bromide.

n-Propyl bromide.

i-Propyl bromide.

n-Butyl bromide.

i-Butyl bromide.

sec-Butyl bromide.

i-Amyl bromide.

Allyl chloride.

Methallyl chloride.

Propargyl bromide.

Benzyl chloride.

B-Phenylethyl bromide.

l -Chloro-2-bromoethane.

In actual application, the organic phosphorothiolates of the present invention may be used singly without incorporation of other ingredients, or, for easier application as controlling chemicals, they may be used in admixture with carriers. The present organic phosphorothiolates are ordinarily formulated, according to procedures thoroughly known to those skilled in the art without necessitating any special conditions,

into such forms as emulsifiable concentrates, wettable powders, oil sprays, dusts, ointments granules,

aerosols, fumigants, etc., and thus can be used in any desired forms using suitable inert carriers. Further, the present organic phosphorothiolates may be used in admixture with one or two or more of other chemicals, whereby the effects thereof can be further broadened. For example, they can be used in combination with organophosphorus type insecticides such as 0,0- dimethyl-S-( 1,2-dicarboethoxy )ethyl phosphorodithioate, O-ethyl O-(4-nitrophenyl)phenyl phosphonothioate, O,6-dimethyl S -(N-methyl carbarnoyl)methyl phosphorodithioate, etc., organochlorine type insecticides such as 'y-Benzene hexachloride, p,p4lichlorodipheny1 trichloroethane, etc.; carbamate type insecticides such as 3,4-dimethylphenyl-N-methylcarbamate, l-naphthyl-N-methylcarbamate, etc.; pyrethroid type insecticides such as allethrin, phthalthrin, etc.; organo-chlorine type fungicides such as pentachlorobenzyl alcohol, pentachlorobenzaldoxime, etc.; organo-sulfur type fungicides; and organo-arsenic type fungicides, and synergistic effects can be expected depending on combinations. Moreover, the present compounds are easily miscible with nematocides, mitecides, herbicides, fertilizers, plant growth-regulators, synergists, attractants, repellents and the like chemicals, whereby multipurpose compositions can be prepared.

The following examples illustrate the invention, however they are not intended to limit the present invention. In the examples, the numerals in the parentheses show the aforesaid numbers representing the present compounds- EXAMPLE 1 Preparation of compound (2):

A solution of 8.4 g. (0.15 mole) of potassium hydroxide in ml. of ethyl alcohol was saturated with hydrogen sulfide to form an ethyl alcohol solution of potassium hydrosulfide. This solution was charged with 48.4 g. (0.15 mole) of 0,0-diethyl-O-(4-phenylpheny1)-thionophosphate, and was then refluxed with stirring for 5 hours. After removing the ethyl alcohol by reduced pressure distillation, a deposited crystal was suspended in ether. Subsequently, the suspension was filtered and then the obtained residue was dried to obtain 40.4 g. of a milky white crystal of potassium O- .ethy1-O4-phenylphenyl phosphorothioate.

33.2 g. (0.1 mole) of this thiophosphate was dissolved in 100 ml. of ethyl alcohol. The resulting solution was charged at room temperature with 15.1 g. (0.11 mole) of sec.-butyl bromide, and was then refluxed with stirring for 7 hours. After removing the solvent by distillation, toluene was added to the residue. The mixture was washed with 5 percent sodium carbonate aqueous solution and then several times with water, and the toluene layer was dried with anhydrous sodium sulfate. Thereafter, the toluene was removed by reduced pressure distillation to obtain 17.2 g. of pale yellow oily substance of O-ethyl-O-(4-phenylphenyD-S-(sec)-butylphosphorothiolate, n

Elementary analysis for C H O PS:

Calculated Found P 8.84 9,03 S (96) 9.15 9.19

' EXAMPLE 2 Preparation of compound l0):

A solution of 33.2 (0.1 mole) of potassium, O- ethyl-(O-4-phenylphenyl)phosphorothioate and 15.1 g. (0.11 mole) of isobutyl bromide in 100 ml. of ethyl alcohol was refluxed with stirring for 3 hours. This solution was treated in a manner similar to that in Example 1 to obtain 16.7 g. of pale yellow oily substance of O- ethyl-O-(4-phenylphenyl)-S-(iso )-butyl phosphorothiolate, n 1.5687.

Elementary analysis for C 1-I,,O,PS:

Calculated Found P 8.84 891 S 9.15 9.43

EXAMPLE 3 Preparation of compound (5 A solution of 34.6 g. (0.1 mole) of a milky white crystal of potassium O-ethyl-O-(4-benzylphenyl)phosphoro-thioate prepared in a manner similar to that in Example 1 and 15.1 g. (0.11 mole) of (sec.)- butyl bromide in 100 ml. of ethyl alcohol was refluxed with stirring for 7 hours. This solution was treated in a manner similar to that in Example 1 to obtain 18.4 g. of yellow oily substance of O-ethyl-O-(4-benzylphenyl)-S- sec.-butylphosphorothiolate, n 1.5490.

Elementary analysis for C,,H,,,O,PS:

Calculated Found P (36) 8.50 8.37 S (96) 8.80 8.89

EXAMPLE 4 Preparation of compound (1 1):

A solution of 34.6 g. (0.1 mole) of potassium O- ethyl-O-(4-benzylphenyl)phosphorothioate and 18.5 g. (0.1 mole) of ,B-phenylethyl bromide in 100 ml. of ethyl alcohol was refluxed with stirring for 4 hours. This solution was treated in a manner similar to that in Example 1 to obtain 33.1 g. of yellow oily substance of O-ethyl- O-(4-benzylphenyl)-S-2-phenylethyl phosphorothiolate, n 1.5725.

Elementary analysis for C l-1, 1%:

Calculated Found P 7.51 7.76 S (11) 7.77 7.93

EXAMPLE Preparation of compound (3):

A solution of 6.0 g. (0.15 mole) of sodium hydroxide in 100 ml. of ethyl alcohol was saturated with hydrogen sulfide to form an ethyl alcohol solution of sodium hydrosulfide. This solution was charged with 41.4 g. (0.15 mole) of 0,0-diethyl-O-2-methoxyphenyl thionophosphate and was refluxed with stirring for 5 hours. After removing the solvent by distillation, the resulting reddish brown oily residue was dissolved in water. Subsequently, the solution was washed 2 times with toluene, and then the water was removed by reduced pressure distillation to obtain 33.0 g. of reddish brown oily sodium O-ethyl-O-(Z-methoxyphenyl)phosphorothioate.

27.0 g. (0.1 mole) of this thiophosphate and 18.5 g. (0.1 mole) of B-phenylethyl bromide were dissolved in 100 ml. of ethyl alcohol, and the solution was refluxed with stirring for 5 hours. This solution was treated in a manner similar to that in Example 1 to obtain 27.8 g. of reddish brown oily O-ethyl-O-(2-methoxyphenyl)-S-2- phenylethyl phosphorothiolate, n 1.5495.

Elementary analysis for C H OJS:

Calculated t Found P (5) 8.79 8.80 S (5) 9.10 9.41

EXAMPLE 6 Preparation of compound (4):

A solution of 27.0 g. (0.1 mole) of sodium O-ethyl- O-( 2-methoxyphenyl)phosphorothioate and 15.1 g. (0.11 mole) of sec.-butyl bromide in 100 ml. of ethyl alcohol was refluxed with stirring for 6 hours. This solution was treated in a manner similar to that in Example 1 to obtain 15.2 g. of reddish brown oily O-ethyl-O-(2- methoxyphenyl)-S-sec.-butyl phosphorothiolate, n

Elementary analysis for C H ORS:

Calculated Found P(%) 10.18 10.45 S(%) 10.53 10.18

EXAMPLE 7 Elementary analysis for C H NO;PS:

Calculated Found P ('11) 9.76 9.62 S(%) 10.10 10.21 N 4.41 4.23

EXAMPLE 8 Preparation of compound (8):

A solution of 29.9 g. (0.1 mole) of potassium O- ethyl-O[3-(N,N-dimethy1amino)-phenyl] phosphorothioate and 18.5 g. (0.1 mole) of B-phenylethyl bromide in 100 ml. of ethyl alcohol was refluxed with stirring for 5 hours. This solution was treated in a manner similar to that in Example 1 to obtain 28.9 g. of reddish brown oily O-ethyl-O-[3-(N,N- dimethylamino)-phenyl]-S-2-phenylethyl phosphorothiolate, n 1.5733.

Elementary analysis for C,.l-l N0,PS:

Calculated Found EXAMPLE 9 Preparation of compound (6):

A solution of 31.3 g. (0.1 mole) of potassium O- ethyl-(4-acetamidephenyl)phosphorothioate obtained in a manner similar to that in Example 5 and 12.7 g. (0.1 mole) of benzyl chloride in ml. of water was stirred at 80C. for 3 hours. This solution was treated in a manner similar to that in Example 1 to obtain 33.9 g. of yellow oily O-ethyl-0-(4-acetamidephenyl)-S-benzyl phosphorothiolate, n 1.5770.

Elementary analysis for C H NOJS:

Calculated Found P 8.48 8.66 S 8.77 8.97 N 3.83 3.73

EXAMPLE 10 Preparation of compound (18):

A solution of 8.4 g. (0.15 mole) of potassium hydroxide in 100 ml. of ethyl alcohol was saturated with hydrogen sulfide to prepare an ethyl alcohol solution of potassium hydrosulfide. This solution was charged with 44.5 g. (0.15 mole) of 0,0-diethyl-O-B-naphthyl thiono-phosphate and was refluxed with stirring for hours. After removing the ethyl alcohol by reduced pressure distillation, a deposited crystal was suspended in ether. The suspension was filtered and then the obtained residue was dried to obtain 36.8 g. of a milky white crystal of potassium O-ethyl-OB-napthyl phosphorothioate, m.p. 85 87C.

30.6 g. (0.1 mole) of this thiophosphate was dissolved in 100 ml. of ethyl alcohol. This solution was charged at room temperature with 14.4 g. (0.1 mole) of l-chloro-2-bromoethane and was refluxed with stirring for hours. This solution was treated in a manner similar to that in Example 1 to obtain 19.9 g. of pale yellow oily O-ethyl-O-B-naphthyl-S-2-chloroethyl phosphorothiolate, r1 1.5907.

Elementary analysis for c,.H...c1o Ps;

Calculated Found P 9.36 9.36 S 9.69 9.89.

EXAMPLE 11 Preparation of compound (16):

A solution of 30.6 g. (0.1 mole) of potassium O- ethyl-O-B-naphthyl phosphorothioate obtained in a manner similar to that in Example 10 and 15.1 g. (0.11 mole) of sec-butyl bromide in 100 ml. of ethyl alcohol was refluxed with stirring for 7 hours. This solution was treated in a manner similar to that in Example 10 to obtain 16.5 g. of yellow oily O-ethyl-O-B-naphthyl-S-sec.- butyl phosphorothiolate, n 1.5832.

Elementary analysis for C I-1 ,0 18:

Calculated Found P 9.55 9.71 S 9.88 10.14

EXAMPLE 12 Preparation of compound 17):

A solution of 30.6 g. (0.1 mole) of potassium O- ethyl-O-B-naphthyl phosphorothioate obtained in a manner similar to that in Example 10 and 13.5 g. (0.1 1 mole) of n-propyl bromide in 100 ml. of ethyl alcohol was refluxed with stirring for 5 hours. This solution was treated in a manner similar to that in Example 10 to obtain 25.2 g. of pale yellow oily O-ethyl-O-B-naphthyl-S- n-propyl phosphorothiolate, n 1.5846.

Elementary analysis for c H O Ps:

Calculated Found EXAMPLE 13 Preparation of compound (19):

A solution of 6.7 g. (0.12 mole) of potassium hydroxide in 50 ml. of ethyl alcohol was saturated with hydrogen sulfide to form an ethyl alcohol solution of potassium hydrosulfide. This solution was charged with 35.6 g. (0.12 mole) of 0,0-diethyl-O-B-naphthyl thionophosphate and was refluxed with stirring for 5 hours. Subsequently, the solution was treated in a manner similar to that in Example 10 to obtain 34.0 g. of a moisture absorptive brown crystal of potassium O- ethyl-O-a-naphthyl phosphorothioate.

30.6 g. (0.1 mole) of this thiophosphate and 18.5 g. (0.1 mole) of B-phenylethyl bromide were dissolved in ml. of ethyl alcohol, and the solution was refluxed with stirring for 4 hours. The solution was treated in a manner similar to that in Example 10 to obtain 26.1 g. of reddish brown oily O-ethyl-O-a-naphthyl-S-Z-phenylethyl phosphorothiolate, n 1.5962.

Elementary analysis for C H O PS:

Calculated Found EXAMPLE 14 Preparation of compound 13):

A solution of 30.6 g. (0.1 mole) of potassium O- ethyl-O-a-naphthyl phosphorothioate and 15.1 g. (0.1 1 mole) of sec-butyl bromide in 100 ml. of ethyl alcohol was refluxed with stirring for 5 hours. Subsequently, the solution was treated in a manner similar to that in Example 10 to obtain 16.7 g. of reddish brown oily O- A solution of 30.6 g. (0.1 mole) of potassium O- ethyl-O-a-naphthyl phosphorothioate and 15.1 g. (0.1 1 mole) of isobutyl bromide in 100 ml. of ethyl alcohol was refluxed with stirring for 3 hours. Subsequently, the solution was treated in a manner similar to that in Example 10 to obtain 15.9 g. of reddish brown oily O- ethyl-O-a-naphthyl-S-iso-butyl phosphorothiolate, n 1.5742. 1 y

Elementary analysis for C H O PS:

Calculated t Found P 9.72 9.55 S 10.03 9.88

EXAMPLE 16 Preparation of emulsifiable concentrates:

The individual compounds set forth in the table below were thoroughly mixed with given proportions of each solvent and emulsifier shown in the table to obtain homogeneous emulsifiable concentrates. In application, the emulsifiable concentrates were diluted with water and the aqueous emulsions were sprayed.

Active ingredient Solvent Emulsifier Compound (2) 50 Xylene 30 *Sorpol 2020 20 (1 l) 20 Cyclohexanone 50 2492 30 (12) 50 Xylene 30 2020 20 (15) 20 Cyclohexanone 50 2492 30 Registered trade name for an emulsifier produced by Toho Chemical Co.

Example 17 Preparation of wettable powder:

40 Parts of the compound and 5 parts of Sorpol 5029 (registered trade name for an emulsifier produced by Toho Chemical Co.) were thoroughly mixed together. The mixture was added drop by drop to, and mixed with, 55 parts of 200 mesh talc under stirring in a mortar, whereby a wettable powder is obtained. in application, the wettable powder was diluted with water and the solution was sprayed.

EXAMPLE 18 Preparation of dusts:

The individual compounds set forth in the table below in such proportions as shown in the table were dissolved in a small amount of acetone. After thoroughly mixing the solutions with 200 mesh talc, the acetone was removed by vaporization to obtain respective dusts. In application, they were dusted as they were.

Active ingredient Extender Compound (1) 2 Talc 98 EXAMPLE 19 Active ingredient Binder Extender Compound (7) 2 Sodium 1 Clay 97 lignosulfonate i. (9) 5 l. 2 u 93 (13m ms "2 93 In order to clarify the excellent characteristics and effects of the present compounds, typical test results are shown below with reference to examples. In the examples, the numerals shown in the parentheses are the numbers representing the compounds exemplified previously.

EXAMPLE 2O Mottled kidney bean plants at the 2 leaves stage, which had elapsed 20 days after the sowing, were parasitized with a large number of two-spotted spider mites (Tetranychus telarius). Subsequently, the leaves of the plants parasitized with said spider mites were dipped for 1 minute in each of aqueous solutions of the present compounds in the form of wettable powders. Thereafter, water was fed so as not to wither the leaves. After 48 hours, the alive and dead of the mites were observed by means of a magnifying glass and, from the mortalities, and Lc 50 values were calculated from the mortality of the mites. The results were as set forth in Table 1.

TABLE 1 Compound No. Le 50 (times) Le 50 (p.p.m.)

(2) 1,200,000 0.834 (3) 640,000 1.563 (4) w (SY 16,000,000 0.063 (10) 1,200,000 0.834 (12 3,000,000 0.333 (12) 2,048,000 0.488 (14) 1,000,000 1.000 (16) 2,000,000 0.500

0,0-dimethyl S-(N- methyl carbarnoy1)- methyl phosphorodithioate 500,000 2.000

Ethyl 4,4'-dichlorobenzilate 100,000 10.000

EXAMPLE 21 Dipping effects on adzuki bean weevils (Callosobruchus chinensis Linne) Adzuki bean weevil adults within 1 day after emergence were dipped for 1 minute in each of aqueous emulsions of the present compounds in the form of emulsifiable concentrates. Subsequently, excess liquid on the surfaces of the weevil bodies was absorbed by means of a filter paper. After 24 hours, the alive and dead of the weevils were observed and Le 50 valueswere calculated from the mortality of the weevils. The results were as set forth in Table 2.

TABLE 2 Compound No. Lc 50 (times) Le 50 (p.p.m.)

0,0-dimethyl O-(-d1methyl 3- methyl 4-nitrophenyl) phosphorothioate 55,000 18.18

0,0-dimethyl S-(1,2-

dicarboethox ethyl) phosphorodi ioate l l ,000 90.91

EXAMPLE 22 Acute oral toxicity to mice.

Each of aqueous emulsions of the present compounds in the form of emulsifiable concentrates was orally administrated to male mice of about 20 g. in body weight. From the mortalities of the mice within a period of 48 hours after the administration, L 50 values were calculated. The results were as set forth in Table 3.

TABLE 3 Compound No. L 50 (mg/k (3) 250 (5) (8) 300 10) 200 12) 100 13) 100 400 (19) 200 0,0-diethyl O-(4-nitro phenyl) phosphorothioate 6 O-ethyl 0-(4-nitro henyl) phenylphosphonot ioate 16 EXAMPLE 23 Full grown northern house mosquito (Culex pipiens pallens) larvae were put into water placed in 500 cc. beakers. Into the water was charged each of the present compounds in the form of granules. After 24 hours, the

alive and dead of the larvae were observed and, from the mortalities thereof, Le 50 values were calculated. The results were as set forth in Table 4.

Rice plants (variety: WASE ASAHI), which had been cultivated to the 3 leaves stage in flower pots of 9 cm. in diameter, were sprayed with 7 ml. per pot of each of given concentration liquids of test compounds. After 1 day, the plants were sprayed to inoculate with a spore suspension of rice blast fungus (Pyricularia oryzae). 4 Days after, the number of disease spots Control value was calculated according to the following equation:

. Number-f Number of spots in spots in nonle-treated treated 1 eaves leaves Value Number of spots in X 100 55 none-treated leaves EXAMPLE 25 insecticidal effects on smaller brown planthoppers 60 (Laodelphax striatellus Fallen) Rice seedlings cm. in height), which had elapsed 15 days after sowing, were dipped for l min. in a diluted emulsion having a given concentration of the emulsifiable concentrate of Example 16. After air-dry- ,5 ing, the seedlings were placed in a large-size test tube. Subsequently, 20 smaller brown planthoppers were released in the tube and then the tube was covered with gauze. After 24 hours, mortalities of the insects were calculated and, from said mortalities, Le

values were calculated. The results were as set forth in Table 6.

TABLE 6 Compound No. Le 50 (times) Le 50 (p.p.m.)

(1) 5 ,000 17.86 (2) 190,000 5.26 (5) 50,000 20.00 (9) 150,000 6.67 (12) 40,000 25.00 (13) 56,000 17.86 (14) 50,000 20.00 (16) 55,000 18.18 0,0-dimethyl S-( 1 ,2- dicarboethoxy) ethyl phosphorodithioate 50,000 20.00 3,5 -xylyl N-methylcarbamate 60,000 16.67

EXAMPLE 26 An emulsion prepared by diluting 50 percent emulsifiable concentrate of the present compound with water to 500 times was spread over young apple trees on which many two-spotted spider mites (Tetranychus telarius Linne) lived in an amount of 150 l/ 1000 m. Before spreading and 3, 5, 7, 11 and 25 days after spreading, the number of the parasitic mites was mea sured to obtain results as shown in Table 7.

TABLE 7 Before After spreading Compound No. spread- 3 5 7 1 1 25 ins days days days days days (1) 160.1 0 0 18.2 59.4 (3) 171.5 1.5 0 5.8 21.4 61.3 (6) 145.8 0 0 9.1 63.8 89.5 (10) 153.1 0.2 1.7 7.3 12.3 41.2 (11) 159.3 0.8 0 2.1 6.8 21.3 0,0-d1methyl S- (1,2-dicarboethoxy ethyl phosphorodithioate 164.9 "0.4 0 3.2 5.3 1 1.1 Control 148.2 193.4 202.3 181.4 174.3 145.1

Note: The figures mean the average number of adults on 10 apple leaves.

EXAMPLE 27 Rice plants at the offshoot stage, which had elapsed 30 days after sowing in pots, were parasitized with about eggs of rice stem borers (Chilo suppresalis Walker). After 4 days, the rice plants were sprayed with 8 ml. per pot of each of aqueous diluted solutions of the present compounds in the form of wettable powders. 5 Days thereafter, the rice stems were broken and the alive and dead of the rice stem borer larvae were observed to calculate the mortalities thereof. The results were as set forth in Table 8. Each mortality is an average value obtained by testing 3 pots.

EXAMPLE 28 Orange fruits, which had been parasitized with a large number of arrowhead scale adults (Pseudococcus comstocki Kuwana), were dipped for 2 minutes in each of aqueous diluted solutions of the present compounds in the form of wettable powders and were allowed to stand for days in a thermostat at C. Subsequently, the scales were stripped off from the fruit surfaces and the alive and dead thereof were observed with a magnifying glass. The results were as set forth in Table 9.

I What is claimed is:

1. Organic phosphorothiolates having the formula,

on V v wherein R is c -c alkyl; A is c -c alkyl, c -c haloalkyl or C -C phenylalkyl; B is a group having the formula,

X being phenyl, C1-C1) phenylalkyl or halogen atom,

provided that at least one X is a group other than halogen atom; and n being an integer of 1-5.

2. The organic phosphorothiolates according to claim 1, wherein the alkyl of R and the alkyl of A are respectively ethyl and n-propyl, secondary butyl or isobutyl.

3. An organic phosphorothiolate of the formula 0 CzHs 4. An organic phosphorothiolate of the formula 5. An organic phosphorothiolate of the formula UNITED STATES PATENT OFFICE- CERTIFICATE OF CORRECTION Patent No. 3,725,514 Dated April 3, 1973 fi oshl TSUCHIYA et al It is certified that error appears in the above-identified 'patent and that said Letters Patent are hereby corrected as shown below:

In Column 12, Table 2, the compound listed as "O',Odime thyl O(*dimethyl 3-methyl 4-nitrophenyl)phos-phorothioate should read:

I 0,0dimethyl O-(3-methyl 4-nitroph enyl)phosphorothioate-.

Signed and sealed this 16th day of July 197a.

(SEAL) Attest:

MCCOY-M. GIBSON, JR. Attesting Officer C. MARSHALL. DANN Commissionerof Patents FORM PO-105O (10-69) 

2. The organic phosphorothiolates according to claim 1, wherein the alkyl of R and the alkyl of A are respectively ethyl and n-propyl, secondary butyl or isobutyl.
 3. An organic phosphorothiolate of the formula
 4. An organic phosphorothiolate of the formula
 5. An organic phosphorothiolate of the formula 